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抑制 MSW 气化合成气燃烧过程中的 CCl 形成:氧化与氯化协同作用和竞争的实验研究。

Inhibition of CCl formation during the combustion of MSW gasification syngas: An experimental study on the synergism and competition between oxidation and chlorination.

机构信息

Institute of Thermal Energy Engineering, Shanghai Jiao Tong University, Shanghai 200240, People's Republic of China.

出版信息

Waste Manag. 2018 Jun;76:472-482. doi: 10.1016/j.wasman.2018.03.027. Epub 2018 Mar 17.

DOI:10.1016/j.wasman.2018.03.027
PMID:29559297
Abstract

For the safe disposal of MSW, a four-step gasification-combustion conversion process is proposed in this work, consisting of material gasification, ash melting, syngas conversion and combustion. Based on the control method of dioxin in gasification process which has been studied previously, experiments of tar chlorination process under oxidative atmospheres were carried out in a homogeneous flow reaction system, using benzene as the tar model compound, to find a way for the inhibition of CCl formation during the syngas combustion process. Results indicated that Cl reacts with benzene more easily than O under low temperatures, and has a positive effect on both oxidative cracking and polymerization. For chlorination reactions, high temperature enhances the chlorination degree and leads to the formation of perchlorinated hydrocarbons, but also promotes the rupture of the weak CCl bonds. With the rise of temperature, hexachlorobenzene became the major product, the amounts of all chlorinated hydrocarbons decreased rapidly, and the conversion direction depended on the amount of O. O generally promotes the formation of hydrogen chloride, and inhibits the chlorination of hydrocarbons. At a temperature above 900 °C, the total amount of chlorinated hydrocarbons was very low under oxidative atmospheres, even only with a equivalence ratio of 0.2. However, during the oxidation process under low temperatures, CCl can also be formed on cyclopentadienyl and 1,3-butadienyl radicals, whose chlorination products were observed. The synergistic and competitive effects between oxidation and chlorination are concluded and the major benzene conversion pathways are summarized according to the products detected.

摘要

为了安全处理城市固体废物,本工作提出了一个四步气化-燃烧转化过程,包括物料气化、灰熔融、合成气转化和燃烧。基于之前研究过的气化过程中二恶英控制方法,在均相流动反应系统中进行了氧化气氛下焦油氯化过程的实验,使用苯作为焦油模型化合物,以寻找在合成气燃烧过程中抑制 CCl 形成的方法。结果表明,在低温下,Cl 比 O 更容易与苯反应,对氧化裂解和聚合都有积极作用。对于氯化反应,高温提高了氯化程度,导致形成全氯化烃,但也促进了较弱的 CCl 键的断裂。随着温度的升高,六氯苯成为主要产物,所有氯化烃的量迅速减少,转化方向取决于 O 的量。O 通常促进氯化氢的形成,并抑制烃类的氯化。在氧化气氛下,温度高于 900°C 时,即使当量比仅为 0.2,总氯化烃的量也非常低。然而,在低温下的氧化过程中,CCl 也可以在环戊二烯基和 1,3-丁二烯基自由基上形成,观察到其氯化产物。根据检测到的产物,总结了氧化和氯化之间的协同和竞争效应,并总结了主要的苯转化途径。

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